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Exploring binding chemistry of alkali/alkaline earth cations in solution through modulation of intramolecular charge-transfer in an excited ambidentate organic fluorophore. | LitMetric

Exploring binding chemistry of alkali/alkaline earth cations in solution through modulation of intramolecular charge-transfer in an excited ambidentate organic fluorophore.

Phys Chem Chem Phys

Grupo de Química Orgánica Medicinal, Facultad de Ciencias, Universidad de la República, 11400 Montevideo, Uruguay.

Published: June 2023

AI Article Synopsis

  • Studying the monoligation of alkali and alkaline earth metal cations in solution is challenging due to their weak binding complexes and lack of effective identification methods.
  • This research demonstrates that tuning the intramolecular charge-transfer (ICT) in a specific fluorophore can be used to assess the binding of these metal cations through straightforward fluorescence techniques.
  • The investigation reveals how different binding functionalities on the fluorophore interact with AM cations, leading to measurable fluorescence responses that help identify binding affinities and interactions based on the Periodic Table positioning of these elements.

Article Abstract

Studying the metal-ligand monoligation of alkali/alkaline earth metals (AMs) in solution represents a significant challenge due to the low stabilization of their complexes and the absence of an effective strategy to identify this type of weak binding. Herein, we show that the modulation of the intramolecular charge-transfer (ICT) in an excited ambidentate organic fluorophore is a convenient strategy to characterize the binding chemistry of AM cations in solution through simple steady-state fluorescence and fluorescence lifetime measurements. The key points of the fluorophore as a metal-binding probe were the location of diverse coordination functionalities with different binding abilities (ionic-, pseudo-covalent- and non-covalent-probes) along the donor-acceptor (D-A) chain and the occurrence of an intramolecular charge-transfer (ICT) mechanism upon excitation. The binding of these functionalities with AM-cations generated selective and specific fluorescence responses, which were quantifiable and allowed us to recognize the primary, secondary and tertiary interactions for all the AM cations in the solution. The relative binding affinities for each one of the functionalities with AM cations was estimated, and a general and consistent perspective of the binding of AMs as a function of their location in the Periodic Table, hardness property and ionic radius was established. The binding preferences of the AM cations were supported by DFT calculations. Our strategy allowed us to validate the binding dynamics of AMs in solution for three types of key ligations, which opens a new perspective to recognize weak intermolecular interactions derived from acidic species and rationally design selective AM-cation probes using an ICT-based ambidentate organic fluorophore.

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Source
http://dx.doi.org/10.1039/d2cp04691aDOI Listing

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